Influence of charge state on product ion mass spectra and the determination of 4S/6S sulfation sequence of chondroitin sulfate oligosaccharides.

Electrospray ionization-Fourier transform ion cyclotron resonance tandem mass spectrometry is used to study the influence of charge state on the product ion spectra of chondroitin sulfate oligosaccharides for determination of the sulfate position on N-acetylgalactosamine residues. Sustained off-resonance irradiation collision-induced dissociation and infrared multiphoton dissociation are investigated for tandem mass spectrometry of chondroitin sulfate. Product ion spectra were obtained for ions of varying charge states from (4,5)-unsaturated (delta-unsaturated), reduced delta-unsaturated, and saturated oligosaccharides from chondroitin sulfate A and chondroitin sulfate C, separately. It was observed that ions in which the charge (z) is less than the number of sulfates dissociate to produce predominantly even-numbered B(n), C(n), Y(n), and Z(n) ions, and that odd-numbered fragment ions are observed for ions that have z equal to the number of sulfates. Sulfate adducted ions were observed in the product ion spectra of singly charged tetramer and hexamer oligosaccharides. This sulfate adduction was determined to result from migration of neutral sulfate during excitation.